Synthesis and pyrolysis behavior of a soluble polymer precursor for ultra-fine zirconium carbide powders

A soluble polymer precursor for ultra-fine zirconium carbide (ZrC) was successfully synthesized using phenol and zirconium tetrachloride as carbon and zirconium sources, respectively. The pyrolysis behavior and structural evolution of the precursor were studied by Fourier transform infrared spectra (FTIR), differential scanning calorimetry, and thermal gravimetric analysis (DSC–TG). The microstructure and composition of the pyrolysis products were characterized by X-ray diffraction (XRD), laser Raman spectroscopy, scanning electron microscope (SEM) and element analysis. The results indicate that the obtained precursor for the ultra-fine ZrC could be a Zr–O–C chain polymer with phenol and acetylacetone as ligands. The pyrolysis products of the precursor mainly consist of intimately mixed amorphous carbon and tetragonal ZrO₂ (t-ZrO₂) in the temperature range of 300–1200 °C. When the pyrolysis temperature rises up to 1300 °C, the precursor starts to transform gradually into ZrC, accompanied by the formation of monoclinic ZrO₂ (m-ZrO₂). The carbothermal reduction reaction between ZrO₂ and carbon has been substantially completed at a relatively low temperature (1500 °C). The obtained ultra-fine ZrC powders exhibit as well-distributed near-spherical grains with sizes ranging from 50 to 100 nm. The amount of oxygen in the ZrC powders could be further reduced by increasing the pyrolysis temperature from 1500 to 1600 °C but unfortunately the obvious agglomeration of the ZrC grains will be induced.     

Phase transformation and nanocrystallite growth behavior of 2 mol% yttria-partially stabilized zirconia (2Y-PSZ) powders

Two mol% yttria-partially stabilized zirconia (2Y-PSZ) precursor powders were obtained through a co-precipitation process using ZrOCl₂.8H₂O and Y(NO₃)₃.6H₂O as starting materials. Phase transformation and crystallite growth behavior have been investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). XRD results show that the crystal structure to be composed of coexisting tetragonal ZrO₂ (t-ZrO₂) and monoclinic ZrO₂ (m-ZrO₂) when the 2Y-PSZ freeze dried precursor powders was calcined at 773–1273 K for 2 h. The fraction of m-ZrO₂ content is lower than 3.0 % when the calcination temperature is lower than 1073 K, whereas m-ZrO₂ content rapidly increases to 8.7 % with the increase of calcination temperature to 1273 K. The crystallite size of t-ZrO₂ increases from 12.3 to 30.2 nm when calcination temperature increased from 773 to 1273 K. In addition, the activation energy of t-ZrO₂ and m-ZrO₂ crytallite growth in 2Y-PSZ freeze dried precursor powders are 29.2 and 21.8 kJ/mol, respectively.     

Ball milling assisted hydrothermal synthesis of ZrO2 nanopowders

The formation of ZrO₂ nanopowders under various hydrothermal conditions such as temperature, time, autoclave rotation speed, heating rate and particularly assistance of ball milling during reaction was investigated. Full ZrO₂ formation (with monoclinic phase) from zirconium solution was completed at shorter times with increasing temperature such as after 4 h at 150 °C, 2 h at 175 °C and less than 2 h at 200 °C. Crystallite size increased from 2.9 to 4 nm with increasing reaction temperature from 125 °C to 200 °C, respectively. Ball milling assisted hydrothermal runs were performed to understand the effect of mechanical force on phase formation, crystallinity and particle size distribution. Monoclinic ZrO₂ was formed in both milled and non-milled runs when zirconium solution was used. Mean particle size for the 2 M solution was measured to be 94 nm for the milled and 117 nm for the non-milled powders. However, when amorphous aqueous zirconia gels (precipitated at pH 5.8) were used, tetragonal phase was also formed in addition to monoclinic phase. Mean particle size was measured to be 0.7 μm (d₉₀≅1.3 μm) for the milled and 7.9 μm (d₉₀≅13 μm) for the non-milled powders. Ball milling during hydrothermal reactions of both zirconium solution and aqueous zirconium gel resulted in smaller crystallite size and mean particle size and, at the same time, effectively controlled particle size distribution (or agglomeration) of nanopowders.     

Synthesis and investigation of properties of nanocrystalline zirconia and hafnia

The effect of the temperature and pH of chemical precipitation on the degree of agglomeration of zirconium and hafnium hydroxides has been investigated. The specific features of crystallization of zirconium and hafnium hydroxides have been revealed. A technological scheme has been proposed for synthesizing ZrO₂ and HfO₂ nanocrystalline powders.     

Long-time ablation protection of carbon/carbon composites with different-La2O3-content modified ZrC coating

Long time oxidation protection at ultra-high temperatures or ablation protection has been a choke point for C/C composites. In this study, long time ablation protection of different-La₂O₃-content (5–30 vol.%) modified ZrC coating for SiC-coated carbon/carbon (C/C) composites was investigated. Results showed that ZrC coating with 15 vol.% La₂O₃ had good ablation resistance and could protect C/C composites for at least 700?s at 2160 °C. A high-thermal-stability and low-oxygen-diffusivity oxide scale containing m-ZrO₂ particles and molten phases with La_0.1Zr_0.9O_1.95 and La₂Zr₂O₇ was formed during ablation, offering the ablation protection. La could erode grain boundaries of ZrO₂ to refine ZrO₂ by short-circuit diffusion and m-ZrO₂ particles were retained due to less bulk diffusion than grain-boundary diffusion of La into ZrO₂. The erosion resulted in the formation of molten phases containing fine nano-ZrO₂, which served as viscous binder among m-ZrO₂ particles and crack sealer for the oxide scale.     

Preparation and characterization of Al2O3–25 mol% ZrO2 composites

Al₂O₃–ZrO₂ (AZ_x), with 25 mol% ZrO₂ content, was prepared using the co-precipitation method. Synthesized powders were characterized by thermal reaction using a differential thermal analysis technique (TG–DTA) and were investigated by phase formation using X-ray diffraction. It indicated that the reaction occurred at 850 °C; cubic (c)-ZrO₂ phase and Al₂O₃ were obtained. By increasing temperature to 1100 °C, tetragonal (t)-ZrO₂ phase was detected. The Al₂O₃–25 mol% ZrO₂ was sintered for 2 h in the temperature range of between 1300 and 1600 °C. The majority phases of ceramics were m-ZrO₂ and α-Al₂O₃, although a t-ZrO₂ phase also appeared as a minor phase and decreased with higher temperature. Moreover, morphology and particle size evolution have been determined via the SEM technique. SEM showed that the particles of powder are agglomerated and basically irregular in shape. An SEM micrograph of ceramics exhibits uniform microstructure without abnormal grain growth.     

Carbothermal production of ZrB2–ZrO2 ceramic powders from ZrO2–B2O3/B system by high-energy ball milling and annealing assisted process

Zirconium diboride (ZrB₂)-zirconium dioxide (ZrO₂) ceramic powders were prepared by comparing two different boron sources as boron oxide (B₂O₃) and elemental boron (B). The production method was high-energy ball milling and subsequent annealing of powder blends containing stoichiometric amounts of ZrO₂, B₂O₃/B powders in the presence of graphite as a reductant. The effects of milling duration (0, 2 and 6 h), annealing duration (6 and 12 h) and annealing temperature (1200–1400 °C) on the formation and microstructure of ceramic powders were investigated. Phase, thermal and microstructural characterizations of the milled and annealed powders were performed by X-ray diffractometer (XRD), differential scanning calorimeter (DSC) and transmission electron microscope (TEM). The formation of ZrB₂ starts after milling for 2 h and annealing at 1300 °C if B₂O₃ is used as boron source and after milling for 2 h and annealing at 1200 °C if B is used as boron source.     

Synthesis of zirconium diboride platelets from mechanically activated ZrCl4 and B powder mixture

ZrB₂ platelets were prepared by mechanochemical processing a zirconium (IV) chloride–boron mixture with subsequent annealing from 800 °C to 1200 °C. The phases present were identified by X-ray diffraction. The size and morphology of the synthesized ZrB₂ powders were characterized by scanning electron and transmission electron microscopy. At 800 °C, ZrO₂ was detected in absence of ZrB₂. At or above 1000 °C, ZrCl₄–B converted to ZrB₂. Moreover, at 1200 °C, ZrCl₄–B completely converted to ZrB₂ without trace quantities of residual ZrO₂. The synthesized ZrB₂ consisted of platelets with a diameter of 0.1–2.1 μm and a thickness of 40–200 nm.     

Sintering of nanocrystalline Ta2O5 and ZrO2 films compared to that of TiO2 films

Thin (d = 60 nm/140 nm) nanocrystalline Ta₂O₅ and ZrO₂ films were deposited onto SiO₂ flakes, using a liquid route synthesis. Their sintering behaviour was characterized and compared to that of the corresponding powders and the known equivalent TiO₂ film in terms of grain size, grain growth and layer porosity. The effect of the substrate was noticeable on crystallisation process but not on grain growth. The sintering behaviour was actually dictated by the initial size and the packing of the precipitated grains related to the synthesis of the film.     

One-pot synthesis of monoclinic ZrO2 nanocrystals under subcritical hydrothermal conditions

This study reports a one-pot synthesis technique for the preparation of single-phase monoclinic zirconium oxide (ZrO₂) nanocrystals. The products were synthesized from only zirconium oxynitrate (ZrO(NO₃)₂) as the precursor under hydrothermal conditions using subcritical water. The precursor was heat-treated in a batch-type reactor at a reaction temperature of 250 °C for 24 h to obtain pure monoclinic-structured ZrO₂ nanocrystals. The crystallization temperature of the ZrO₂ phase was also greater than 200 °C. However, the products of reactions conducted at 200 °C for 24 h were mixtures of the tetragonal and monoclinic structures. At a reaction temperature of 250 °C, the volume fraction of the monoclinic phase increased; however, the reaction time was also important. The heat-treatment was performed for more than 12 h in order to obtain single-phase monoclinic ZrO₂ nanocrystals. The crystallite size of this product was approximately 20 nm, and water, hydroxide groups, and nitro groups were chemisorbed on its surface.     

Synthesis of nanosized zirconium carbide powders by a combinational method of sol–gel and pulse current heating

Zirconium carbide nanopowders were synthesized by a novel method combining the advantages of sol–gel method and rapid synthesis using pulse current heating. The core-shelled structure of ZrO₂/C mixture was obtained during the sol–gel process, and further heat treatment in SPS led to the fast formation of ZrC. The particle size of ZrO₂ played an important role in the synthesis of nanosized ZrC powders. In addition, the coalescence and grain growth of ZrC particles could be also limited due to the fast heating rate. As a result, the reactions were thoroughly completed at a relatively low temperature and ZrC nanopowders of 60–100 nm were obtained. The corresponding powders also had low oxygen content (∼0.64 wt%) and residual carbon content (∼0.27 wt%). Additive-free ZrC powders could be sintered to ∼99% relative density with an average grain size of 0.8 μm at low temperature of 1750 °C.     

Synthesis of nanosized zirconium carbide by a sol–gel route

Nanosized zirconium carbide was synthesized by a new simple sol–gel method using zirconium n-propoxide, acetic acid as chemical modifier, and saccharose as carbon source. When heat-treated at 900 °C under flowing argon, gels transformed into intimately mixed amorphous carbon and nanosized tetragonal ZrO₂. Further heat treatments above 1200 °C led to the formation of zirconium carbide with some dissolved oxygen in the lattice. Oxygen content could be reduced by increasing the heat treatment temperature from 1400 to 1600 °C, which unfortunately also induced a mean crystallites size increase from 90 to 150 nm. Short heat treatments above 1600 °C were carried out to further purify the samples and to limit the particles growth. A compromise between purity and average crystallite's size could then be found. Powders were assessed using X-ray diffraction, thermal analysis and scanning electron microscopy.     

Room-temperature UV-ozone assisted solution process for zirconium oxide films with high dielectric properties

A facile, low-cost, and room-temperature UV-ozone (UVO) assisted solution process was employed to prepare zirconium oxide (ZrO_x) films with high dielectric properties. ZrO_x films were deposited by a simple spin-coating of zirconium acetylacetonate (ZrAcAc) precursor in the environment-friendly solvent of ethanol. The smooth and amorphous ZrO_x films by UVO exhibit average visible transmittances over 90% and energy bandgap of 5.7 eV. Low leakage current of 6.0 × 10⁻⁸ A/cm² at 3 MV/cm and high dielectric constant of 13 (100 Hz) were achieved for ZrO_x dielectrics at the nearly room temperature. Moreover, a fully room-temperature solution-processed oxide thin films transistor (TFT) with UVO assisted ZrO_x dielectric films achieved acceptable performances, such as a low operating voltage of 3 V, high carrier mobility of 1.65 cm² V⁻¹ s⁻¹, and on/off current ratio about 10⁴–10⁵. Our work indicates that simple room-temperature UVO is highly potential for low-temperature, solution-processed and high-performance oxide films and devices.     

Synthesis and characterization of bioactive zirconia toughened alumina doped with HAp and fluoride compounds

Alumina–zirconia nanostructured composites (ZrO₂ addition by 20 wt%) were prepared using combined gelation–precipitation process. A modified sol–gel process has been developed to prepare nano structured spinel [MgAl₂O₄], Al₂O₃, ZrO₂ and their composite materials. This process is useful in retaining tetragonal phase of zirconia at room temperature, which provides transformation toughening in the nano composites. Dried gels powders were calcined up to 1250 °C. Similarly, hydroxyapatite powders were produced by wet-chemical method and calcined at different temperatures. All the dried gel and calcined powders were characterized by using X-ray diffraction, DTA/TGA and SEM. Samples were prepared by uniaxial pressing the composites powders using ZTA, HAp, MgF₂ and CaF₂ in different ratio. Incorporation of CaF₂ and MgF₂ as a source for fluorine was also done to improve the sinterability of composites. The samples were sintered at 1400 °C for three hours. Densification and mechanical behaviour of sintered samples were observed. Bioactivities of all compositions were tested using SBF solution and then characterizing by FTIR. The main objective of work was to dope ZTA nano composites with HAp and fluoride compounds to obtain better sinterability at lower temperatures. Then evaluate the obtained ZTA based bioactive composite ceramics that have high mechanical strengths. This study verifies the bioactivities of HAp-added ZTA composites.     

Reaction and phases from monoclinic zirconia and calcium aluminate cement at high temperatures

Solid state reaction using m-ZrO₂ and high alumina cement as starting materials was studied. Various compositions containing different proportions of calcium aluminate cement (5–50 mol% CaO in ZrO₂) were reaction sintered at 1300–1500 °C. Crystalline phase formation and densification of Ca stabilized ZrO₂ composites was investigated by X-ray diffraction analysis, density and shrinkage measurements. Scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy was used to examine the microstructure. The main crystalline phases formed are related to the expected with the equilibrium phase diagram of the ZrO₂–CaO–Al₂O₃ system. Stabilized c-ZrO₂ is formed with the composition of Ca_0.15Zr_0.85O_1.85. The sintering of the mixtures leads to porous composites materials. Textural properties were analyzed considering the initial composition and the present crystalline phases.     

Solvent effect on synthesis of zirconia support for tungstated zirconia catalysts

Solvothermal reaction of zirconium n-butoxide (ZNB) in different solvent media, such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol resulted in the formation of zirconium dioxide (ZrO₂) nanostructure. Then, the 15%W/ZrO₂ (WZ) catalysts using different zirconia supports were prepared by impregnation method. The effects of solvent on preparation of zirconia on the catalytic performance of WZ catalysts in esterification of acetic acid and methanol at 60 °C were investigated. The experimental results showed that ZrO₂ particles prepared in 1,4-butanediol (ZrO₂-BG) have a spherical shape, while in other glycols the samples were irregularly-shaped particles. The reaction results of esterification illustrated that the W/ZrO₂-BG catalysts had high surface acidity and showed high acetic acid conversion. The W/ZrO₂-PeG catalysts (ZrO₂ particles prepared in 1,5-pentanediol, PeG) exhibited the lowest surface acidity among other samples due to strong interaction of proton species and the zirconia supports as proven by TGA. One of the possible reasons can be attributed to different amounts of carbon residue on the surface of catalysts.     

Fabrication and abrasive wear behavior of ZrO2-SiC-Al2O3 ceramic

In this paper, ZrO₂-SiC-Al₂O₃ ceramic was fabricated by as-prepared ZrO₂-SiC powders and commercial α-Al₂O₃ powders, sintered at 1450 °C for 1 h. ZrO₂-SiC composite powders were synthesized through carbothermal reduction with zircon as raw material and carbon black as the reductant. Through ZrO₂-SiC-Al₂O₃ ceramic mechanical properties measurements it was indicated that this ceramic had excellent properties in both bending strength and hardness. In addition, ZrO₂-SiC-Al₂O₃ ceramic abrasive wear property was measured. ZrO₂-SiC-Al₂O₃ ceramic mass loss increased along with the increase in both wheel rate and applied load. The type of wear particles had an important effect on abrasive wear resistance. ZrO₂-SiC-Al₂O₃ ceramic displayed excellent abrasive wear resistance in bentonite and quartz slurries in comparison with SiC slurry.     

Fabrication of well-crystallized mesoporous ZrO2 thin films via Pluronic P123 templated sol–gel route

Mesoporous zirconia (ZrO₂) thin films were prepared by dip-coating via Pluronic P123 templated sol–gel route. ZrOCl₂·8 H₂O was used as zirconium (Zr) precursors. Annealing of as-coated ZrO₂ thin films is important in order to stiffen the respective films and to remove the Pluronic P123. The mesoporous structure and crystallite size of ZrO₂ were characterized systematically by field-emission scanning electron microscope (FESEM), both low- and wide-angle X-ray diffraction, thermal analysis technique and Brunauer–Emmett–Teller method. At annealing temperature of 400 °C, amorphous ZrO₂ was transformed into tetragonal phase of ZrO₂ (t-ZrO₂). At 450 °C, t-ZrO₂ and monoclinic phase of ZrO₂ (m-ZrO₂) were obtained. By altering heating rate during annealing, volume fraction of t-ZrO₂ and m-ZrO₂ was changed. FESEM images showed that disordered mesostructures of ZrO₂ were formed after annealing. The surface area of mesoporous ZrO₂ obtained ranges from 54.33 to 93.39 m²/g.     

Effect of high alumina cement on permeability and structure properties of ZrO2 composites

Porous ZrO₂ based ceramics are widely used for filtration/separation processes due to the good chemical and thermal stability. For these applications it is desirable that the material have a controlled porous structure in order to obtain good permeability. In this study Ca stabilized ZrO₂ composites were developed from a starting mixture of pure ZrO₂ containing different mole proportions of calcium aluminate cement. Ceramics disks were uniaxially pressed and subsequently sintered at 1300–1450 °C. The influence of process parameters such as chemical compositions and sintering temperature on textural characteristics (volume fraction of pores, pore size distribution) and permeability was followed by apparent density measurements, Hg porosimetry and N₂ permeation, respectively. Sintered microstructure was examined by scanning electron microscopy SEM. The XRD analysis showed that m-ZrO₂ transformed to tetragonal and/or cubic ZrO₂, these phases probably coexisted at relatively low CaO addition. For 30 mol% addition, amount of the cubic Ca_0.15Zr_0.85O_1.85 phase appreciably increased. At 50 mol% CaO, CA₂ was the major phase of the composite with minor CaZrO₃ formation whereas relative content c-ZrO₂ is slightly reduced.The composites had 30–40 vol% porosity with typical pore radius of 1–1.3 μm and the corresponding Darcian permeability k₁ values varied between 2 and 4 × 10^?14 m², such structure parameters slightly increased for high cement addition. The k₁ of ceramics produced from 50 mol% CaO composition remained nearly constant up to 1450 °C due to similar densification degree. The experimental permeability dependence on pore structure parameters as well as the comparison with the value estimated by Ergun's equation are showed.     

Stirring speed assisted homogenization of precipitation reaction for enhanced optical performance of Y2O3 transparent ceramics

Y₂O₃ transparent ceramics were fabricated from precipitated powders prepared at different stirring speeds during the precipitation process. The influence of the stirring speed on the phase component of precursors, morphology of Y₂O₃ powders and properties of fabricated ceramics were systematically investigated. Crystalline phase precursors of (NH₄)_aY(OH)_b(CO₃)_c·H₂O were prepared from 110 rpm, 220 rpm and 550 rpm respectively. But amorphous precursors of Y(CO₃)(OH)·nH₂O (n = 1–1.5) were observed when stirring speeds were 330 rpm and 440 rpm. Y₂O₃ powders prepared from 440 rpm exhibited the lowest agglomeration and the smallest grain size, and the ceramics with the optimal transmittance was accordingly obtained. The results of computational fluid dynamics software CFX showed that a more homogeneous flow field distribution without local circulations could be produced at 440 rpm, which would be benefit for the optical quality of transparent ceramics. The study would provide a considerable reference for the controllable fabrication of well-dispersibility Y₂O₃ powders and Y₂O₃ transparent ceramics.